Bis-anthrols and bis-naphthols and diglycidyl ethers thereof

ABSTRACT

Certain bis-anthrols and bis-naphthols and their diglycidyl ethers are novel and useful in the preparation of new polyether thermoplastic compositions. The compounds have the formulae: ##STR1## (or its keto tautomer) or ##STR2## where A is as defined in the claims.

FIELD OF THE INVENTION

The present invention relates to new bis-anthrols and bis-naphthols andto glycidyl ethers thereof.

BACKGROUND OF THE INVENTION

A variety of bis-phenols are known in the art which are used to preparepolyethers by reaction with epichlorohydrin. For example, U.S. Pat. No.3,410,825 describes certain bis[p-(2,3-epoxypropoxy) phenyl] polycyclichydrocarbons and polyethers thereof. The resulting polyethers are usefulin such applications as molding, extrusion, adhesives, coatings and thelike. However, the various polyethers must be highly crosslinked toimprove their high temperature properties for certain uses, such as bythe aerospace industry, but such high crosslinking results in generallylower toughness. What is needed is a resin system that combines the goodproperty advantages of excellent high temperature properties along withhigh toughness and also good processability (extrusion) by athermosetting resin technique.

Certain bis-anthrols and bis-naphthols are known in the art as inJedlinski et al., Przemyslu Chem., 46(5), 272-274 (1967); Beilstein, 6,1053; E2, 1028; Morgan, Macromolecules, 3, 536 (1970) and Chen, Journalof Applied Polymer Science, 27, 3292 (1982). Such materials have foundlittle, if any, use in the polymer art and not for polyethers havinguseful properties, e.g., the aerospace industry. Accordingly, there is aneed for new resins which could be prepared from new monomers whichwould provide structural components to give new properties to polyetherresins.

SUMMARY OF THE INVENTION

The present invention is directed to new bis-anthrols and bis-naphtholsof the formulas Ia and Ib or the keto tautomer of Ia ##STR3## wherein X¹and X² each independently is an alkyl group containing 1 to 4 carbonatoms or a halogen atom having an atomic number of from 9 to 35,inclusive; m is 0, 1 or 2; n is 0, 1, 2, 3 or 4; and A is a divalenthydrocarbon radical selected from the group consisting of an alylenegroup containing from 3 to 8 carbon atoms, or a radical derived from anon-aromatic carbocyclic group or a dialkyl aromatic or non-aromaticcarbocyclic group containing from 7 to 24 carbon atoms in which eachalkyl group contains from 1 to 8 carbon atoms and the carbocyclic groupcomprises a central non-aromatic ring containing 5 to 7 carbon atoms ina ring or a central aromatic carbocyclic ring, each central ringoptionally bridged or fused with a non-aromatic or aromatic carbocyclicring. When A is a dialkyl aromatic or non-aromatic carbocyclic group itshould be understood that the bonds from A to the anthrol or naphtholgroup are from the alkyl substituents of the dialkyl carbocyclic group.

In the compounds of Formulas Ia and Ib, X¹ and X² each independently isan alkyl group containing from 1-4 carbon atoms such as methyl, ethyl orthe like or a halogen atom having an atomic number of from 9 to 35 suchas chlorine or fluorine. Preferably, when X¹ or X² is present, each is amethyl group or a chlorine atom. m is 0, 1 or 2 and preferably 0 or 1; nis 0, 1, 2, 3 or 4 and preferably each of m and n independently is 0or 1. In one embodiments, m and n are both 0.

A is a group selected from an alkylene group containing from 3 to 8carbon atoms; or a non-aromatic carbocyclic group or a dialkyl aromaticor non-aromatic group containing from 7 to 24 carbon atoms and a centralnon-aromatic ring containing 5 to 7 carbon atoms in a ring or a centralaromatic carbocyclic ring, each central ring optionally bridged or fusedon each side with a non-aromatic or aromatic carbocyclic ring. In onepreferred embodiment, A is derived from a dialkylaromatic carbocyclicgroup containing 12 to 20 carbon atoms in which each alkyl groupcontains from 3 to 5 carbon atoms, and the anthrol or naphthol isattached to the alkyl substituent of the dialkylaromatic carbocyclicgroup. The alkylene, carbocyclic and dialkylcarbocyclic groups include2,2-isopropylidene, anthrylene, fluorenylene,phenylene-diisopropylidene, norcamphanylidene, adamantylene,naphthylene, and equivalent kinds of groups. Preferably, A isnaphthylene-diisopropylidene or phenylenediisopropylidene.

Bis-naphthols are preferred because they are easier to use as monomersand diglycidyl ethers and the resulting polyethers are also easier tohandle and have very desirable mechanical properties.

The bis-anthrols of Formula Ia and the bis-naphthols of Formula Ib areprepared by alkylating the appropriately X_(m) ¹ and X_(n) ² substitutedor unsubstituted 9-anthrols or 1-naphthol with conventional bis orhigher functionality alkylating agents. Suitable alkylating agentsinclude olefins, alcohols, halogenated hydrocarbons, carbonyl compoundsand the like. For example, the alkylating agent isp-diisopropenylbenzene, bis-p-(1-hydroxy-1-methylethyl) benzene,bis-p-(1-chloro-1-methylethyl) benzene and the like. Bis-anthrols arealso prepared by alkylating the corresponding 9-anthrone via its9-hydroxy intermediate, particularly with a bis-alcohol alkylatingagent.

The alkylations are conducted by conventional procedures known in theart for the alkylation of aromatic alcohols or carbonyl compounds. Forexample, the 9-anthrols or 1-naphthols are treated with the appropriatebis-tertiary alcohol compound, e.g.,bis-p-(1-hydroxy-1-methylethyl)benzene, in the presence of1,1,1-trichloro-ethane, p-toluenesulfonic acid or hydrochloric acid andthe like and optionally 3-mercaptopropionic acid at reflux. In the caseof the 1-naphthol, the alkylation occurs unexpectedly almost exclusivelyat the position ortho to the phenolic hydroxyl group.

The present invention is also directed to a diglycidyl ether of abis-anthrol or a bis-naphthol of the Formula IIa and IIb or of the ketotautomer of Ia. ##STR4## wherein A has the same meaning and preferencesas set forth in Formulas Ia and Ib above.

The diglycidyl ethers of the bis-anthrols or bis-naphthols of Formula Iaor Ib can be prepared by treating a bis-anthrol or a bis-naphthol withepichlorohydrin or epibromohydrin in the presence of a strong base suchas sodium hydroxide or the like as is conventionally known in the artfor the glycidylation of phenols. The reaction is usually conductedunder relatively mild conditions of temperature and pressure. Forexample, the reaction can be conducted at from about 20° C. to about120° C. at normal pressure. Depending on the solubility of thebis-anthrol or bis-naphthol, the reaction is conducted in the absence orpresence of conventional alcohol, ether, ester or aromatic or aliphatichydrocarbon solvents and the like. For example, the reaction isconducted at about 50° C. to 90° C. in a solvent such as diethyl ether,toluene, xylene, ethyl acetate, ethyl isobutyrate, ethanol or,especially, isopropanol.

In the case of bis-anthrols, the keto tautomer tends to be the primaryproduct unless the reaction is controlled in favor of the bis-phenoltautomer, e.g., by generating bis-phenate ion prior to adding theepihalohydrin using potassium tertiary-butoxide in slight excess of thebis-anthrol.

The bis-naphthols and their diglycidyl ethers are purified and recoveredby conventional techniques of solvent extraction and the like. Thebis-anthrols and their digylcidyl ethers are somewhat difficult topurify by solvent extraction and may require the use of conventionalchromatographic techniques if highly pure materials are required.

The diglycidyl ethers of bis-anthrol or bis-naphthol having the FormulaIIa or IIb are useful to prepare various conventional kinds of polymers,such as polyether amines and polyethers, including high melting, highmolecular weight polyethers, composed essentially of recurring linearunits of Formula III. ##STR5## which are homopolymers or are copolymerswherein at least a minor amount, e.g., 10 mole percent, of Y is thegroup remaining after removal of the terminal hydroxy groups frombis-anthrol or bis-naphthol of Formula Ia or Ib above wherein A, X¹, X²,m and n have the meanings previously shown and a major amount, e.g., notmore than 90 mole percent, of Y is the group remaining after removal ofthe terminal hydroxy groups from a different bis-phenol compoundincluding a different bis-anthrol, bis-naphthol or a conventionalbis-phenol including those illustrated herein after.

The curable linear molecules of polyether or polyether aminecompositions are prepared by (1) reacting a bis-anthrol or bis-naphtholof Formula Ia or Ib above with a different conventional bis-phenolcomponent or diglycidyl ether thereof and optionally a multifunctionalphenol or amine in the presence of base or (2) alternatively reacting adiglycidyl ether of a bis-anthrol or bis-naphthol alone or (a) also witha conventional bis-phenol in the presence of base or (b) with adi-secondary amine component alone and optionally a multifunctionalphenol or amine. These molecules can be with or without lightcrosslinking.

A preferred use of the compounds of Formulas Ia or Ib and IIa or IIb ofthe invention is to make (co)polyether thermoplastic compositions havingflexible portions and bulky stiff portions, prepared by reacting adiepoxide of a bis-hydroxy compound with a bis-phenol compound or anamine to form linear molecules and lightly cross-linking the resultinglinear molecule. Such polyether and polyether amine thermoplasticcompositions are broadly but not specifically disclosed in copendingU.S. patent application Ser. Nos. 871,950 with amines, 871,951 and871,952, all filed June 9, 1986, the disclosures of which areincorporated by reference and representatively illustrated in detailbelow in which the flexible portions and bulky stiff portions can bederived from the bis-anthrols or bis-naphthols or diglycidyl ethersthereof, which compounds comprise the present invention.

The compounds of the invention can be used in polyether thermoplasticcompositions including, for example, those linear molecules having therepeating structure ##STR6## (a) "X" and "Y" represent a segmentcomprising stiff units (SU) and optional flexible units (FU), whichstiff units and flexible units are interconnected;

(b) said stiff units, SU and SU', are independently selected from thegroup consisting of substituted and non-substituted aromatic rings,cycloaliphatic rings and heterocyclic rings;

(c) said flexible units which permit rotation at an angle, FU and FU',are independently selected from the group consisting of ##STR7## (d) thenumber of "X" segments in said molecules are "a", the number of "Y"segments in said molecules are "b", and the ratio of ##EQU1## is betweenzero and one; (e) the ratio of the number of stiff units to flexibleunits in said "X" segment (SU/FU) is equal to or greater than the ratioof the number of stiff units to flexible units in said flexible "Y"segment (SU'/FU');

(f) the number of stiff units and flexible units are selected such thatthe average number of total stiff units ##EQU2## divided by the averagenumber of total flexible units ##EQU3## is greater than zero; andpreferably (g) said composition having a glass transition temperature ofat least about 150° C., a flex modulus of at least 350 KSI and afracture toughness of at least 1000 psi √in.

Such polyethers can be prepared by conventional techniques including aprocess comprising reacting:

(a) a first component selected from the group consisting of bis-phenolcompounds of the formula HO--X--OH, where X and Y are defined above with

(b) a second component, said second component being a diepoxide selectedfrom the group consisting of ##STR8## wherein if the phenol compound isHO--X--OH, then the diepoxide is chosen from the structure of FormulaVII or VIII and if the phenol compound is HO--Y--OH, then the diepoxideis chosen from the structure of Formula VII; and

(c) a catalytic amount, preferably of 0.1 mole per mole of said firstcomponent, of a basic condensation catalyst at a temperature of about130° to about 230° C. for about 1 to about 24 hours and with a molarratio of phenol compounds to diepoxides preferably of about 0.90:1 toabout 1.04:1 until the desired linear reaction product has been formed,and thereafter stopping the reaction.

A. Bis-phenol Component

In a preferred embodiment the bis-phenol components employed have thestructure HO--X--OH or HO--Y--OH where "X" and "Y" are specified above.

When the bis-anthrols and bis-naphthols of Formula Ia and Ib and/ortheir glycidyl ethers of Formula IIa and IIb are used in the abovecompositions, the ratio (f) the number of stiff units and flexible unitsare selected such that the average number of total stiff units ##EQU4##divided by the average number of total flexible units ##EQU5## isgreater than zero; is preferably from about 1.5 to about 20 andespecially from about 2 to about 10.

As a practical matter, it is preferred that the bis-phenol componentcontain the "X" segment, i.e., that the phenol component be HO--X--OH.The reason for this is that it is usually easier to synthesize thebis-phenol component (containing the relatively large number of stiffunits) than it is to glycidate the corresponding diphenol compound. Inparticular, it is preferred to employ diepoxides based on BPA and usebis-phenol compounds based on the less common compounds. However, incertain cases it may be preferable to have the segment X, in thediepoxide component since the diepoxide may have alower melting pointthan the bis-phenol component, resulting in an easier thermoplasticpolymer synthesis, especially if it is desired to perform the synthesisin the melt as opposed to a solution preparation.

The stiff units which can be used in the polymers prepared from thebis-anthrols and bis-naphthols or their glycidyl ethers of the inventionare selection from the group consisting of substituted ornon-substituted aromatic rings, cycloaliphatic rings and heterocyclicrings. The aromatic rings are inertly substitued or unsubstitutedbenzene radicals. Substituted benzene radicals have substituents whichdo not interfere in the process independently selected from the groupconsisting of Cl, Br or C₁ -C₅ alkyl groups.

A group of bis-phenol compounds are aromatic, cycloaliphatic orheterocyclic rings including those of Formulas Ia and Ib of theinvention and those shown below: ##STR9## This particular illustratedgroup of bis-phenol compounds are distinguished from bis-phenolcompounds such as BPA and the like, by the presence of 2 or moreflexible units ##STR10## and 3 or more stiff units ##STR11##

If desired, the bis-phenol compounds described above can be substitutedin the polyethers in part (or even in whole in certain cases) with otherconventional bis-phenols, represented by the formula ##STR12## in whichR and R¹ when taken collectively with the connector carbon C areselected from the group consisting of cyclohexyl and alkyl-substitutedcyclohexyl, and when taken separately are from the group consisting ofhydrogen, alkyl, cyclohexyl, phenyl, alkyl-substituted cyclohexyl, alkylsubstituted phenyl, halogen substituted cyclohexyl and haloensubstituted phenyl groups with the total number of carbon atoms in thegroup or groups attached to said connector carbon atom not exceedingeighteen and the number of carbon atoms in any of said alkyl substituentgroups not exceeding six.

B. Diepoxide Component

The second reactant in the condensation process, the diepoxide is acompound having two vicinal expoxide groups (oxirane rings) in terminal(or optionally non-terminal) positions in the molecule, usually in theform of an oxygen atom bound to two terminal carbons of an alkyl group,though the epoxide may also be on a ring, such as a cyclohexyl ring.Suitable diepoxides are terminal diepoxyalkanes, e.g., 1,2-epoxy-3,4-epoxybutane, 1,2-epoxy-5,6-epoxyhexane, 1,2-epoxy-7,8-epoxyoctane andthe like. Others are terminal diepoxides containing ether linkages, suchas bis(2,3-epoxypropyl)ether and bis(2,3-epoxy-2-methylpropyl) ether;diglycidyl ethers of alpha,omega glycols such as the diglycidyl ethersof ethylene glycol, trimethylene glycol, and tetramethylene glycol; anddiglycidyl ethers of dihydric phenols.

Diglycidyl ethers of the dihydric phenols referred to above aregenerally suitable for use in this invention. One may suitably use thediglycidyl ether of the same phenol which is employed as the otherreactant. Thus, for example, bis-phenol diisopropylbenzene is suitablycondensed with diglycidyl ether of alpha,alpha'-bis(1-hydroxy-2-naphthyl)-p-diisopropylbenzene. Useful resins canalso be prepared by condensing a dihydric phenol with the diglycidylether of a different dihydric phenol. For example, useful condensationproducts have been prepared according to this invention from thediglycidyl ether of bisphenol A and the dihydric phenol alpha,alpha'-bis(1-hydroxy-2-naphthyl)-p-diisopropylbenzene.

In preparing the products of this invention the epoxy reagent may be apure diepoxide or a crude mixture containing a substantial proportion ofdiepoxide, e.g., 70% or more. It is important, however, that the crudereagent is free of monoepoxide and of monohydric alcohol or phenol.

C. Amine Component

The amine component employed in making the polymers of the presentinvention is selected from the group consisting of primary amines orpreferably a bis secondary amine or mixtures thereof.

The primary amines will have the general formula ##STR13## or a mixturethereof where "X" and "Y" are the "X" segments or "Y" segments referredto before.

The bis secondary amines will have the general formula: ##STR14## or amixture thereof where "X" and "Y" segments or "Y" segments referred tobefore and R and R' are unsubstituted or inertly substituted C₁ -C₂₀aliphatic, cycloaliphatic or aromatic hydrocarbyl groups. Preferably Rand R are C₁ -C₂₀ aliphatic, cycloaliphatic or aromatic hydrocarbylgroups. Preferably R and R' are C₁ -C₂₀ alklyl groups. Examples of R andR' include methyl, ethyl, isopropyl, cyclohexyl, benzyl, tolyl and thelike.

Examples of primary monoamines include aniline (phenylamine),2,6-dimethylaniline, 2,4-dimethylaniline, 2,6-diethylaniline,N-aminophthalimide, 2,6-diisopropylaniline, tolylamine,alpha-naphthylamine, 3-amino-benzothiophene, 1-aminoadamantane, andnorbornylamine. Preferred primary monoamines include aniline,2,6-dimethylaniline and 2,6-diethylaniline with 2,6-diethylaniline beingmost preferred.

Examples of bis secondary amines includeN,N'-dimethyl-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine,bis(N-sec-butyl-4-aminophenyl)-methane, alpha,alpha'-bis(N-methyl-4-aminophenyl)-p-diisopropylbenzene, alpha,alpha'-bis(N-sec-butyl-4-aminophenyl)-p-diisopropylbenzene,9,9-bis(N-methyl-4-aminophenyl)-fluorine,N,N'-dimethyl-4,4'-diaminodiphenyl sulfone, and alpha,alpha'-bis(1-amino-2-naphthyl)-para-diisopropylbenzene.

The amine-base resins preferably comprise linear molecules having therepeating structure ##STR15## where A is selected from the groupconsisting of ##STR16## and mixtures thereof and B is selected from thegroup consisting of ##STR17## where R and R' are selected from the groupconsisting of unsubstituted or inertly substituted C₁ -C₂₀ aliphatic,cycloaliphatic or aromatic hydrocarbyl groups, and X and Y are definedabove.

Whe preparing copolymers, the reaction is typically carried out in themelt although it is more convenient in solution in a solvent. Desiredhigh impact resistance is a property which can require complete removalof solvent. In the production of resin for use in molding, extrusion,and the like, solvent is removed from the reaction mixture. In theproduction of resin for surface coatings, the resin may remainassociated with solvent until it is actually applied as a coating andthe solvent is removed by evaporation under suitable conditions. Itsboiling point should be such that the reaction can be carried out at 75°to 150° C. at a practical pressure. The solvent may be a mixture ofindividual compounds. Useful solvents which meet those criteria are, forexample, certain ketones, halogenated hydrocarbons and ethers. Methylethyl ketone is a preferred solvent. Cyclohexanone, methyl isobutylketone and the other ketones may be used. Chloroform, 1,2-dichloroethaneand other chlorinated hydrocarbons may be used, particularly inadmixture with ketones. Ethers, such as dioxane, tetrahydrofuran,dimethoxyethane and lower alkyl (methyl or ethyl) ethers of ethyleneglycol are suitable, alone or in admixture with ketones. Other solventswhich meet the above criteria may be employed if desired, such asN-methyl pyrrolidone.

While in the examples which follow the synthesis was performed insolution, it is possible (and desirable in some cases) to do thesynthesis in the absence of solvent, i.e., as a melt. In such cases itmay be desirable to use the diepoxide containing the "X" segment sincethe melting point of diepoxide component is usually much lower than themelting point of the corresponding bis-phenol component.

LIGHT CROSSLINKING

Light crosslinking refers to the crosslinking of between 1 and 50 out ofeach 100 repeat units to repeat units of other molecules, e.g., FormulasI or II of said thermoplastic polymer. Preferably, the crosslinkingdensity is between 2 and 20 out of 100, more preferably between about 3and 10 repeat units per 100 units. There are basically three differentconventional techniques that can be used to obtain lightly crosslinkedmatrices: (1) the use of a slightly greater number of diepoxide groupsthan phenolic or secondary amine groups (see earlier section on Catalystand Reaction Conditions). When using this technique the repeat unitswill crosslink through the reaction of the secondary hydroxyl groupswith the remaining epoxide groups. Once the thermo plastic polymer isprepared, it may be used alone or with a reinforcing fiber in anFRC-type (fiber reinforced composite) composition, wherein the polymermass is heated to an elevated temperature (e.g., above 170° C.) and heldat that temperature for the necessary time (typically about 2 to about24 hours) to obtain crosslinking; (2) incorporate an appropriate amountof multifunctional (tri- or higher) epoxide or multifunctional (tri- orhigher) phenolic or amine in the preparations of the thermoplasticpolymer. The crosslinking agent, when added as a separate component,replaces a portion of the phenolic component or the epoxide component,as desired. For example, if 20% crosslinking agent is used, then 20% ofthe phenolic or secondary amine component is replaced on an equivalentbasis.

Examples of suitable multifunctional epoxide polymers include EPON®Resin 1031 and EPON Resin DPS-164. EPON Resin DPS-164 has the generalformula ##STR18## where n equals an average of 3. EPON Resin 1031 hasthe structure ##STR19##

Other crosslinking agents include multifunctional amines such as EPONHPT™ Curing Agents 1061 and 1062, having the molecular structure:##STR20## where R is H for CA 1061 and R is CH₃ for CA 1062.

Still other crosslinking agents include ##STR21## and ##STR22##

(3) The addition of crosslinking agents, such as triepoxides, etc., tothe resulting thermoplastic polymer.

The amount of crosslinking agent chosen is selected to achieve thedesired level of light crosslinking, as opposed to the normalcrosslinking used for epoxy resins. Accordingly, when using acrosslinking agent such as EPON Resin 1031, the amount of equivalentsused is 2 to 20%. Likewise, when the crosslinking agent is EPON HPTCuring Agent 1061, the amount of equivalents used is 5-50%.

While light crosslinked polymers are preferred, full crosslinked ornon-crosslinked polymers are within the scope of this invention.

The composition optionally, but preferably for high-performanceapplications such as automotive and aerospace, contains a reinforcingsubstrate. Suitable reinforcing materials include, for example, glassfibers, carbon fibers, Kevlar, boron, calcium carbonate, talc, alumina,asbestos and the like. The preferred fibrous reinforcing material forhigh-performance applications is selected from the group consisting ofglass fibers, carbon fibers, boron fibers and Kevlar fibers, withcontinuous carbon fiber being most preferred. The fibrous reinforcingmaterial will be present in the composition in an amount effective toimpart increased strength to the cured composition, generally from about40 to about 95 weight percent, usually from about 60 to about 80 weightpercent, based on the weight of the total composition.

The polyether or polyether amine resin composition can be applied to thefibrous reinforcing material from the melt or solution by methods knownin the art. Among the various processes useful with the presentinvention include resin transfer molding (RTM), pultrusion, filamentwinding and the use of pre-pregs. Such methods are known in the art, andare disclosed, for example, in the Handbook of Composites, Lubin, Ed.,Van Nostrand Reinhold Company, 1982, pages 321-532, and in the book byDelmonte titled Technology of Carbon and Graphite Fiber Composites,Delmonte, Van Nostrand Reinhold Company, 1981.

On method of current preferred interest involves the use of pre-pregs.In that system, the polymer composition/curing agent-impregnatedsubstrate, or "pre-preg", or a laminate prepared from a plurality ofpre-pregs, is then cured. When the system is based on a polyether of thediglycidyl ether of alpha,alpha'-bis(1-hydroxy-2-naphthyl)-p-diisopropylbenzene and bis-phenoldiisopropylbenzene, the curing is typically accomplished at atemperature of about 150° to about 200° C. for about 1 to about 16 hoursunder vacuum or under a presence of 1 atmosphere to 150 psi, to form thestructural composite article.

The polyether resin compositions have particular application in theaerospace industry where the high performance obtainable with thepresent invention is required. In particular, RTM may be used to preparelarge parts, such as helicopter blades. Pre-pregs may be used tu prepareparts such as wings and the like. Filament winding may be used toprepare an entire fuselage, while pultrusion may be used to prepareparts having a constant cross section. The composition can optionallyinclude additives for control or modification of various properties ofthe composition in its cured or uncured state, including cure rateaccelerators or retardants, tackifiers and the like.

ILLUSTRATIVE EMBODIMENTS

To illustrate the present invention, the following illustrativeembodiments are given. It is to be understood, however, that theembodiments and examples are given for the purpose of illustration onlyand the invention is not to be regarded as limited to any of thespecific materials or conditions used in the specific embodiments.

Embodiment 1-α,α'-bis(10-anthr-9-one)-p-diisopropylbenzene (BADB)

BADB was synthesized by charging a stirred reactor with anthrone, p-diol[bis-p-(1-hydroxy-1-methylethyl)benzene] and 1,1,2-trichloroethane in amolar ratio of 4:1:7 and heating to 100° C. under nitrogen and refluxcondenser. Concentrated aqueous HCl (1.02 moles as 100% HCl/mole p-diol)was charged at 100° C. with an addition funnel. BADB was recovered byfiltration and purified by washing with methanl, slurrying in boilingtoluene, filtering and washing with methanol again. The yield was about60% of fine yellow crystals with melting point-255°-265° C. The chemicalstructure of BADB was confirmed by C13 solid state NMR.

Embodiment 2-Diglycidyl α,α'-bis(10-anthr-9-one)-p-diisopropylbenzene(DGBADB)

DGBADB was synthesized by charging a stirred reactor with BADB ofEmbodiment 1, potassium t-butoxide (KTBA), and toluene in a molar ratioof 1:2.4:65 and heating to 110° C. for 1 hour under nitrogen. T-butanolwas continuously removed as the toluene azeotrope and fresh tolueneadded back to the reactor. The reaction mass remained a slurrythroughout this step, but the color changed from yellow to crimson redas the potassium salt of BADB was formed. After 1 hour at 110° C., thered slurry was cooled to 40° C. Epichlorohydrin (20-200 moles/mole BADB)was charged all at once with an addition funnel and the mass was reacted60-90 minutes at 70° C. During this step the red BADB salt went intosolution and crystals of KCl and uncovered BADB crystallize out. Thecrude product was recovered by first cooling the reaction mass andallowing the solids to settle. The supernatent was decanted through afilter and the product recovered by vacuum evaporating at 100° C.maximum (no longer than 10 minutes at this temperature) under 1-5 mm Hgvacuum. The crude product was dissolved 20% wt. in methylisobutyl ketone(MIBK) and water washed until the wash water was neutral. The finalproduct was recovered by vacuum evaporating the MIBK. The DGBADBobtained had a weight per epoxy equivalent (WPE)=395-450 (theoreticalWPE=331), sponifiable chlorine (Sap Cl)=0.01% wt., and meltingpoint=160°-170° C. The chemical structure of DGBADB was supported by C13solution NMR end group analysis experiments.

Embodiment 3-9,9-bis(1-hydroxy-2-naphthyl)-fluorene (BNFL)

BNFL was synthesized by charging 1-naphthyl, 9-fluorenone,1,1,1-trichloroethane, p-toluenesulfonic acid, and 3-mercaptopropionicacid to a stirred reactor in a molar ratio of 8:1:4:0.5:0.1 and heatedto 90° C. for 2 hours under nitrogen and reflux condenser. After 5minutes at 90° C. crystals formed in the reaction mass. When thereaction mass went solid with crystals, more 1,1,1-trichloroethane wasadded and the reaction was continued. The reaction mass was cooled bythe addition of a portion of isopropyl alcohol (IPA) and the productremoved by filtration and washed with IPA. BNFL was obtained in 91%yield as white crystals with melting point=268°-290° C. The chemicalstructure for BNFL was supported by C13 and Proton solution NMR.

Embodiment 4-α,α'-bis(1-hydroxy-2-naphthyl)-p-diisopropylbenzene (BNDB)

BNDB was synthesized by charging 1-naphthol, p-diol as[bis-p-(1-hydroxy-1-methylethyl)benzene], and 1,1,2- or1,1,1-trichloroethane to a stirred reactor in a molar ratio of 8:1:4 andheating to 70° C. under nitrogen and a reflux condenser. Concentratedaqueous HCl (1.02 moles as 100% HCl:mole p-diol) was charged at 70° C.with an addition funnel. The reaction mass was heated at 80° C. for 1hour after the addition of the HCl was complete. BNDB begancrystallizing out of the reaction mass 10-15 minutes after the first HClwas added. At the end of 1 hour, the reactor was thick with BNDBcrystals. IPA was added as the slurry was cooled to aid in filtration ofthe BNDB. BNDB was collected by filtration and washed several times(until white) with IPA. The filtrate was slurried in boiling IPA andcollected by filtration again. The white crystalline BNDB (90-95%yield), melting point=245°-255° C., was of suitable purity for makingthe epoxy resin. BNDB was also recrystallized out of tetrahydrofuran(14% wt. BNDB). The chemical structure of BNDB was confirmed by C13 andProton solution NMR, X-ray Diffraction and Mid-Infra Red experiments.

Embodiment 5-Diglycidyl ofα,α'-bis(1-hydroxy-2-naphthyl)-p-diisopropylbenzene (DGBNDB)

DGBNDB is made by charging BNDB, epichlorohydrin (ECH), iospropanol(IPA), and water to a stirred reactor in a molar ratio of1.0:15.0:13.5:12.0 and heating to 70° C. under nitrogen and a refluxcondenser. At 70° C. the reaction mass was a slurry. 20% wt. sodiumhydroxide (3.0 moles sodium hydroxide per mole of BNDB) was added to thehot reaction mass in stages over 80 minutes. BNDB had reacted intosolution by the end of the first NaOH addition period. The organic phasewas washed with hot-deionized water until the wash water was neutral. Asthe organic phase cooled and became more concentrated, DGBNDB had atendency to crystallize out of solution. The DGBNDB containing organicphase was vacuum evaporated to give the desired product with a WPE=316,Sap Cl=0.04-0.06% wt. The product was dissolved in methyl-isobutylketone (MIBK), 20-30% wt. resin, and doing a second dehydrohalogenationreaction using 5% wt. aqueous NaOH. The resin solution was heated 2hours at reflux under nitrogen with 20-25% wt. (based on the wt. of theresin solution) of 5% wt. aqueous NaOH. The brine was removed and theresin solution washed with hot de-ionized water until the wash water wasneutral. The hot resin solution was filtered to remove any insolublematerial, and then concentrated by distillation to approximately 50% wt.resin. DGBNDB crystallized out as the solution cooled and was collectedby filtration. The white crystalline DGBNDB had a WPE=281 (theoreticalWPE=279), Sap cl=<0.01% wt., and melting point=167°-168° C. The chemicalstructure of DGBNDB was confirmed by C13 and Proton solution NMR.

Embodiment 6

A variety of phenolic and amine curing agents was used to polymerize thediglycidyl ethers of the invention as follows:

DGBNDB/amine polymers were made by dissolving the monomers in a vacuumerlenmyer flask at 190° C. at the desired stoichiometry and treatingwith the curing agent. Mixing was facilitated by pulling pump vacuum(1-5 mm Hg vacuum) on the erlenmyer and degassing while dissolutionoccurred. In the case of DGBNDB-based polymers made by a phenolic cure,MBTPP (methylene-bis-triphenylphosphine dibromide; 0.0024 equivalentsBr/equivalent epoxy) was added after the monomers were dissolved andhomogeneous. The polymers (unless otherwise noted) were cured at 190° C.for 24 hours in a forced draft oven.

The prepolymer mixtures were poured between preheated glass plates whichhad been pretreated with Surfasil™ Siliconizing Agent (Pierce ChemicalCompany). The glass plates were separated by 1/8 in. teflon bead in ahorseshoe shape and were clamped together. Typical casting size for afull spectrum of mechanical testing was 40 grams. The resultingcompositions are set forth in the table below.

    ______________________________________                                                   Curing Agent                                                                              Ratio of Phenol (P)                                    Diglycidyl or          or Amine (NH) to                                       Ether      Co-monomer  Epoxide (E)                                            ______________________________________                                        DGBNDB     NMADB       NH/E = 1.0                                             DGBNDB     NMADB       NH/E = 1.0                                                        13% ADB                                                            DGBNDB     NMADB       NH/E = 1.0                                                        26% ADB                                                            DGBNDB     NMADB       NH/E = 1.0                                                        50% ADB                                                            DGBNDB     NMADB       NH/E = 1.0                                                        75% ADB                                                            DGBNDB     ADB         NH/E = 1.0                                             DGBNDB     BPDB        P/E = 1.0                                                         15% TPTB                                                           DGBNDB     BPDB        P/E = 1.0                                                         25% TPTB                                                           DGBNDB     BPDB        P/E = 1.0                                                         35% TPTB                                                           DGBNDB     BPDB        P/E = 1.0                                                         50% TPTB                                                           DGBNDB     BPDB        P/E = 1.0                                                         75% TPTB                                                           DGBNDB     BPDB         P/E = 0.96                                            DGBNDB     BPA          P/E = 0.96                                            DGBNDB     DMA         NH/E = 1.0                                                        15% DMADB                                                          DGBNDB     THQ         NH/E = 1.0                                                        15% ADB                                                            DGBNDB     NBMDA       NH/E = 1.0                                                        25% MDA                                                            DGBNDB     NBMDA       NH/E = 1.0                                                        50% MDA                                                            ______________________________________                                         DGBNDB Diglycidyl ether of alpha,                                             alphabis(1-hydroxy-2-napthyl)-p-diisopropylbenzene                            NMADB alpha, alphabis(N--methyl4-aminophenyl)-p-diisopropylbenzene            ADB alpha, alphabis(4-aminophenyl)-p-diisopropylbenzene (EPON Curing Agen     HPT 1061)                                                                     BPDB alpha, alphabis(4-hydroxyphenyl)-p-diisopropylbenzene                    TPTB alpha, alpha', alphatris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene      BPA 2,2bis(4-hydroxyphenyl)propane                                            DMA 2,6dimethylaniline                                                        DMADB alpha, alphabis(4-amino-3,5-dimethylphenyl)-p-dissopropylbenzene        (EPON Curing Agent HPT 1062)                                                  NBMDA N,N.sup.1 --disec-butyl methylene dianiline                             THQ 1,2,3,4tetrahydroquinoxaline                                         

The polymer compositions were tested according to the following testprocedures:

Flexural properties of neat resins were evaluated according to ASTM D790method using 1/8 in. thick specimens. Specimens were tested both in Dry(at Room Temperature and ˜75% R.H.) and Hot/Wet (after immersion inboiling water for 48 hours, test at 200° F., 5 min. equilibration time)conditions.

Fracture toughness, K_(q), was measured using mini-compact tensionspecimens (see W. B. Jones, et. a. Am. Chem. Soc. Soc., Div. Polym.Chem., Polym. Prepr., 22, 1981). All specimens were slotted to a Chevronshape and then precracked with a razor blade.

Tensile properties were measured according to ASTM D638 method.

Swelling in solvents was evaluated by measuring weight gain per unit ofinitial weight after immersion in solvent for a specified time at roomtemperature.

The resulting polyether thermoplastic compositions had thecharacteristics of a thermosetting polymer along with an improvedbalance of properties including solvent resistance and improvedmodules/glass transition temperature/toughness balance as determined bythe test procedures set forth above.

What is claimed is:
 1. A bis-anthrol or a bis-naphthol of the formula Iaor Ib or the keto tautomer of Ia ##STR23## wherein X¹ and X² eachindependently is an alkyl group containing from 1 to 4 carbon atoms or ahalogen atom having an atomic number of from 9 to 35, inclusive; m is 0,1 or 2; n is 0, 1, 2, 3 or 4; and A is a divalent dialkyl aromatic ordialkyl non-aromatic carbocyclic group containing from 7 to 24 carbonatoms in which each alkyl group contains from 1 to 8 carbon atoms and inwhich the carbocyclic comprises (1) a central non-aromatic carbocyclicring containing 5 to 7 carbon atoms in a ring, or (2) a central aromaticcarbocyclic ring, wherein the central ring of (1) or (2) may be bridgedor fused with one or two non-aromatic or aromatic carbocyclic rings; andwherein the anthrol or naphthol group is directly attached to alkylsubstituents of the dialkyl carbocyclic group.
 2. A bis-anthrol or abis-naphthol according to claim 1 wherein X¹ and X² are eachindependently methyl groups or chlorine atoms.
 3. A bis-anthrol or abis-naphthol according to claim 2 wherein m and n are
 0. 4. Abis-anthrol or a bis-naphthol according to claim 3 wherein A is aphenylene-p-diisopropylidene group or a naphthylenediisopropylidenegroup.
 5. A bis-naphthol according to claim 4 wherein A is aphenylene-p-diisopropylidene group.
 6. A bis-naphthol according to claim4, wherein A is a naphthylene-diisopropylidene group. 7.9,9-bis(1-hydroxy-2-naphthyl)fluorene.